Low density surface sites are believed to play an important role in processes occurring on oxide surfaces, including catalysis and particle and film nucleation. However, our understanding of the role and chemical nature of such sites play in these processes is limited by the inability to experimentally detect minority surface sites in many oxide systems. The research performed for this dissertation is focused on developing a surface science technique utilizing fluorescent molecules to titrate specific surface sites on planar fused silica surfaces in an ultra-high vacuum (UHV) environment. High sensitivity (low detection limit) is achieved by using derivatives of perylene, a high quantum yield fluorophore. High specificity is attained by employing perylene derivatives with functional groups designed to react chemically with and titrate various sites. In addition to titrating the well-studied hydroxyl sites with perylene-3-methanol (density ~ 10¹⁴ cm⁻²), which is used to establish the technique, the detection of strained siloxane sites (~ 10¹² cm⁻²), ) with perylene-3-methanamine and oxygen vacancy sites (~ 10¹¹ cm⁻²), ) with 3-vinyl perylene is demonstrated. Particle nucleation on oxides is suspected to involve defects that trap adatoms and form critical nuclei. Using this technique, the possible role strained siloxane and oxygen vacancy sites play in trapping adatoms during the nucleation of Ge nanoparticles on silica surfaces is examined. / text